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The Volyn biota, fossilized organisms with a minimum age of 1.5 Ga, were found in cavities in granitic pegmatites from the Korosten Pluton, NW Ukrainian shield. Fossilization was due to an influx of hydrothermal fluorine-rich waters, which silicified the outermost part of the organisms, thus preserving the 3D morphology. Details of the morphology (investigated by scanning electron microscopy) show that the majority of the specimens are filamentous, of a large variety with diameters ranging from ∼ 10 to ∼ 200 µm, thin filaments with typical branching and thick filaments with ball-shaped outgrowths and dented surface. Filaments can be straight or conical, curvilinear, or strongly curved, up to millimeters in length, some with a central channel. Some filaments show indications of segmentation and are grown as sessile organisms onto substrate; others show both intact ends, indicating a non-sessile, free-living lifestyle. Objects with flaky morphology and agglutinating filaments are interpreted as fossil biofilms. Other objects are hollow and show a large variety of forms; spherical objects are scarce. Infrared spectroscopy indicates the presence of chitosan in one filament type, electron microprobe analysis of nanometer-sized inclusions in filaments identified the presence of Bi(Te,S) minerals, and both observations are compatible with the interpretation as fungi-like organisms. Stable C- and N-isotope data of bulk samples are in the range of −31 ‰ to −47 ‰ δ13C and of +3 ‰ to +10 ‰ δ15N, indicating possible methanogens as part of the subsurface microecosystem. The Volyn biota indicate that at 1.5 Ga complex forms of life existed in the continental deep biosphere, well above the microscopic level, including fungi-like organisms resembling eukaryotes.

The chemical selectivity and faradaic efficiency of high‐index Cu facets for the CO2 reduction reaction (CO2RR) is investigated. More specifically, shape‐controlled nanoparticles enclosed by Cu {hk0} facets are fabricated using Cu multilayer deposition at three distinct layer thicknesses on the surface facets of Au truncated ditetragonal nanoprisms (Au DTPs). Au DTPs are shapes enclosed by 12 high‐index {310} facets. Facet angle analysis confirms DTP geometry. Elemental mapping analysis shows Cu surface layers are uniformly distributed on the Au {310} facets of the DTPs. The 7 nm Au@Cu DTPs high‐index {hk0} facets exhibit a CH4 : CO product ratio of almost 10 : 1 compared to a 1 : 1 ratio for the reference 7 nm Au@Cu nanoparticles (NPs). Operando Fourier transform infrared spectroscopy spectra disclose reactive adsorbed *CO as the main intermediate, whereas CO stripping experiments reveal the high‐index facets enhance the *CO formation followed by rapid desorption or hydrogenation.

The Volyn biota, fossilized organisms with a minimum age of 1.5 Ga, were found in cavities in granitic pegmatites from the Korosten pluton, NW Ukrainian shield. Fossilization was due to influx of hydrothermal fluorine-rich waters, which silicified the outermost part of the organisms, thus preserving the 3D morphology. Details of the morphology (investigated by scanning electron microscopy) show that the majority of the specimens is filamentous, of a large variety with diameters ranging from ~10 µm to ~200 µm, thin filaments with typical branching, thick filaments with ball-shaped outgrowths and dented surface. Filaments can be straight or conical, curvilinear or strongly curved, up to mm in length, some with a central channel. Some filaments show indications for segmentation, are grown as sessile organisms onto substrate; others show both intact ends, indicating growth in soft medium or floating in water. Objects with flaky morphology and agglutinating filaments are interpreted as fossil biofilms. Other objects are hollow and show a large variety of forms; spherical objects are scarce. Infrared spectroscopy indicates the presence of chitosan in one filament, electron microprobe analysis of nm-sized inclusions in filaments identified the presence of Bi(Te,S) minerals, and both observations are compatible with the interpretation of filaments as fungi-like organisms. Stable C- and N-isotope data of bulk samples are in the range of -31 to -47 ‰ δ13C/12C, and of +3 to +10 ‰ δ15N/14N, indicating possible methanogenic bacteria as part of the subsurface micro-ecosystem. The Volyn biota show that at 1.5 Ga fungi-like organisms lived in the continental deep biosphere, where complex forms of life existed, well above the microscopic level.

The Volyn biota, a distinct example of 3D-preservation of ~1.5 Ga old Precambrian fossils from huge cavities in granitic rocks as a habitat for microorganisms in the deep biosphere, consist of several different types of organisms. Most common are filaments of variable diameter (10 µm-range to 100 µm-range) and length up to cm. Branching, segmentation, outgrowths, and a central channel are typical. Ends can be simple rounded, thinning out, or with outgrowths. Filaments grew on mineral substrate (?sessile organisms); filaments with two ends indicate growth in soft clay media or floating in water. Spherical objects in the size of tens of µm could represent spores or other types of seeds. For larger objects, some with conical shape, in the 100 µm-range, no recent analogue is obvious. Bi(S,Te) nm-minerals in filaments, either irregularly distributed or in rod-like arrangement, have an analogue in recent fungi, but also in other microorganisms. Objects with flaky to irregular shape are reminiscent of a former biofilm. Filaments are also partly covered with a sheath, interpreted as extracellular protein substance. d 13C/12C-isotope values of approximately -40 ‰ to -50 ‰, typical for methanogenic bacteria, and a range of d 15N/14N-isotope values of +2‰ to +9 ‰ also indicate different organisms. The crucial fact for the excellent 3D-preservation of the microfossils is their occurrence in cavities of igneous rocks, which preserved them from further diagenetic-metamorphic overprint as common in sediments. These microfossils give an impressive insight into Precambrian life in the deep biosphere.

We report on Precambrian microfossils from igneous rocks of the Volyn pegmatite district, associated with the Paleoproterozoic Korosten pluton, northwestern Ukraine. The fossils were recovered from meter-sized miarolitic cavities and show a well-preserved 3D morphology, mostly filamentous but with a large variety of types and also in irregular, flaky shapes reminiscent of former biofilms, as well as rare spherical objects. Based on literature data, pyrolysis experiments, and reflected light microscopy results, the organic matter (OM) is characterized as (oxy-)kerite. Further investigations with microscopic techniques, including scanning and transmission electron microscopy, and electron microprobe analysis show that fossilization likely occurred during a hydrothermal, post-pegmatitic event by silicification dominantly in the outermost 1–2 µm of the microfossils. The hydrothermal fluid, derived from the pegmatitic environment, was enriched in SiF4, Al, Ca, Na, K, Cl, and S. The OM shows O enrichment in which N and S content is low, indicating simultaneous N and S loss during anaerobic oxidation. Mineralization with Al silicates starts at the rim of the microfossils, continuing in its outer parts into identifiable encrustations and intergrowths of clay minerals, feldspar, Ca sulfate, Ca phosphate, Fe sulfide, and fluorite. Breccias, formed during collapse of some the miarolitic cavities, contain decaying OM, which released high concentrations of dissolved NH4+, responsible for the late-stage formation of tobelite-rich muscovite and buddingtonite. The age of the fossils can be restricted to the time between the pegmatite formation, at ∼1.760 Ga, and the breccia formation at ∼1.49 Ga. As the geological environment for the growth of the microorganisms and fossilization, we assume a geyser system in which the essential biological components C, N, S, and P for growth of the organisms in the miarolitic cavities were derived from microorganisms at the surface. Fossilization was induced by magmatic SiF4-rich fluids. The Volyn occurrence is a distinct and uncommon example of Precambrian fossils, and the results underline the importance of cavities in granitic rocks as a possible habitat for microorganisms preserved in the deep biosphere.

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. Polyhedron Ag nanostructures were created on top of a polished Au electrode via step-wise electrodeposition and tested as substrates for SERS spectroscopy. Average Raman enhancement factors were derived by combining SERS measurements with electrochemical impedance spectroscopy (EIS), which is able to determine the electroactive surface area of a randomly nanostructured surface. Depending on the deposition step an alternating increase and decrease of surface area was observed while the SERS intensity showed a clear maximum for the first deposition cycle. SEM pictures reveal the formation of Ag polyhedrons that are randomly dispersed on the Au surface. Furthermore the presence of a sub nanostructure on top of the polyhedron after the first deposition cycle is observed which becomes smoother after subsequent deposition cycles. Correlating the SEM pictures with SERS and EIS measurements it is concluded that the coral-like sub nanostructure is dominating the enhancement factor while the polyhedron structure itself only plays a minor role for electromagnetic field enhancement.

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. Covalent attachment of a microporous polymer network (MPN) on a gold surface is presented. A functional bromophenyl-based self-assembled monolayer (SAM) formed on the gold surface acts as co-monomer in the polymerisation of the MPN yielding homogeneous and robust coatings. Covalent binding of the films to the electrode is confirmed by SEIRAS measurements.

Mc 2009. Microscopy Conference, Graz, Austria. 30 August - 4 September 2009. First Joint Meeting Of Dreiländertagung And Multinational Congress On Microscopy.